Processes for producing hydrocarbons from a renewable feedstock

ABSTRACT

Processes for the production of linear alkylbenzenes from a renewable feedstock. Prior to converting the side chains of the glycerides and free fatty acids of the feedstock into hydrocarbons, the feedstock is separated into a stream rich in C 10  and C 14  free fatty acids glycerides having C 10  and C 14  fatty acid side chains and at least one, preferably two, other glyceride streams. The stream rich in glycerides having C 10  and C 14  fatty acid side chains can be converted via deoxygenation into a stream rich in C 9  to C 14  hydrocarbons while the other glyceride streams can be used as vegetable oil. A C 10  to C 13  hydrocarbon fraction from the stream rich in C 9  to C 14  hydrocarbons may be dehydrogenated to form olefins which may be reacted with benzene to form linear alkylbenzenes. The linear alkylbenzenes may be used to produce surfactants.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority from Provisional Application No.62/199,709 filed Jul. 31, 2015, the contents of which are herebyincorporated by reference

FIELD OF THE INVENTION

The present invention relates generally to methods for producinghydrocarbons from a renewable feedstock to be used, for example asdetergent compounds, and more particularly relates to methods forproducing linear alkylbenzenes, paraffins, and olefins from natural oilsand kerosene.

BACKGROUND OF THE INVENTION

Linear alkylbenzenes (LABs) are organic compounds with the formulaC₆H₅C_(n)H_(2n+1). While “n” can have any practical value, currentcommercial use of alkylbenzenes requires that n lie in the range of 10to 16, or in the range of 8 to 15, or in the range of 10 to 13, or inthe range of 12 to 15, or in the range of 9 to 14. These specific rangesare often required when the alkylbenzenes are used as intermediates inthe production of surfactants for detergents. Since the surfactantscreated from alkylbenzenes are biodegradable, the production ofalkylbenzenes has grown rapidly since their initial uses in detergentproduction in the 1960s. The linearity of the paraffin chain in thealkylbenzenes is key to the material's biodegradability andeffectiveness as a detergent. A major factor in the final linearity ofthe alkylbenzenes is the linearity of the paraffin component.

While detergents made utilizing alkylbenzene-based surfactants arebiodegradable, many processes for creating alkylbenzenes are notentirely based on renewable sources. Specifically, alkylbenzenes arecurrently produced from kerosene derived from petroleum that wasextracted from the earth. U.S. Pat. Nos. 3,950,448 and 5,276,231 bothdisclose processes from the production of linear alkylbenzenes fromfossil fuel feedstocks. In these processes, linear hydrocarbons andbenzene may be combined to form the linear alkylbenzenes. The linearhydrocarbons and benzene may be derived from the processing of petroleumcrude oil. However, there is increasing interest in producing chemicals,such as linear alkylbenzenes, from feedstocks other than from petroleumcrude oil, at least in part due to the cost uncertainty and limitedsupply of the petroleum crude oil.

Accordingly, various advances have resulted in processes which produce alinear hydrocarbons from renewable feedstocks having glycerides andfatty acids. The linear hydrocarbon produced by such process can be usedin a variety of applications including the production of linearalkylbenzenes. For the production of linear alkylbenzenes, typicallyonly C₁₀ to C₁₃ normal paraffins are desired. Other normal paraffinsproduced outside of the C₁₄ to C₁₈ range are generally desirable fordiesel fuel or diesel fuel blending component. Since these hydrocarbons,both larger and smaller, are not desired for linear alkylbenzenes, theprocessing and treatment of the larger hydrocarbons consumes resourcesand increases expenses and, therefore, may be not be desired.

Therefore, it would be desirable to have one or more processes forproviding a linear hydrocarbons in a desired range suitable for use toproduce linear alkylbenzenes while reducing the production andprocessing of undesirable hydrocarbons.

SUMMARY OF THE INVENTION

One or more processes have been invented for the production of a linearalkylbenzene, paraffin, or olefin product from a natural oil in whichonly a desired range of fatty acids are converted into hydrocarbons.

Therefore, in a first aspect of the invention, the present invention maybe characterized broadly as providing a process for producing a linearhydrocarbon for use in producing a linear alkylbenzene surfactant by:separating a renewable glyceride feedstock in a fractionation zone intoa triglyceride stream rich in C₁₀ to C₁₄ fatty acid side chains and atleast one other glyceride steam; deoxygenating the triglyceride streamrich in C₁₀ to C₁₄ fatty acid side chains in a deoxygenation zone havinga catalyst and being operated under deoxygenation conditions to providea paraffin hydrocarbon stream; dehydrogenating the paraffin hydrocarbonstream in a dehydrogenation zone to provide an olefin hydrocarbonstream; and, alkylating the olefin hydrocarbon stream with an aromatichydrocarbon stream in an alkylation zone having an alkylation catalystand being operated under alkylation conditions to provide an alkylbenzene product stream.

In at least one embodiment of the present invention, the fractionationzone comprises at least one fractionation column.

In one or more embodiments of the present invention, the fractionationzone provides the triglyceride stream rich in C₁₀ to C₁₄ fatty acid sidechains, a heavy glyceride steam, and a light glyceride stream. It iscontemplated that the process includes recovering at least one of theheavy glyceride stream and the light glyceride stream to be used asvegetable oil. It is further contemplated that the process includesrecovering both the heavy glyceride steam and the light glyceride streamto be used as vegetable oil.

In various embodiments of the present invention, the renewable glyceridefeedstock comprises an oil rich in triglycerides with C₁₀ to C₁₄ fattyacids. It is contemplated that the oil rich in triglycerides with C₁₀ toC₁₄ fatty acids is selected from the group consisting of: coconut oil;palm kernel oil; laurel oil; babassu oil; microbial oils; and mixturesthereof.

In one or more embodiments of the present invention, the processincludes sulfonating the alkyl benzene product stream to provide asurfactant product.

In a second aspect of the present invention, the present invention maybe broadly characterized as providing a process for producing a linearhydrocarbon for use in producing a linear alkylbenzene surfactant by:passing a renewable glyceride feedstock to a fractionation zone toseparate the renewable glyceride feedstock into a triglyceride streamrich in C₁₀ to C₁₄ fatty acid side chains and at least one otherglyceride steam; passing the triglyceride stream rich in C₁₀ to C₁₄fatty acid side chains to a deoxygenation zone having a catalyst andbeing operated under deoxygenation conditions to provide a paraffinhydrocarbon stream; passing the paraffin hydrocarbon stream to adehydrogenation zone to provide an olefin hydrocarbon stream; and,passing the olefin hydrocarbon stream and an aromatic hydrocarbon streamcomprising benzene to an alkylation zone having an alkylation catalystand being operated under alkylation conditions to provide an alkylbenzene product stream.

In one or more embodiments of the present invention, the processincludes: sulfonating the alkyl benzene product stream to provide asurfactant product. It is contemplated that the fractionation zoneprovides the triglyceride stream rich in C₁₀ to C₁₄ fatty acid sidechains, a heavy glyceride stream, and a light glyceride stream. It isalso contemplated that the process includes recovering at least one ofthe heavy glyceride stream and the light glyceride stream to be used asvegetable oil.

In some embodiments of the present invention, the process includesrecovering both the heavy glyceride stream and the light glyceridestream to be used as vegetable oil.

In various embodiments of the present invention, the renewable glyceridefeedstock is selected from the group consisting of: coconut oil; palmkernel oil; laurel oil; babassu oil; microbial oils; and, mixturesthereof.

In at least one embodiment of the present invention, the renewableglyceride feedstock comprises an oil rich in glycerides having C₁₀ toC₁₄ fatty acid side chains.

In one or more embodiments of the present invention, the fractionationzone comprises a fractionation column. It is contemplated that thefractionation column provides a light glyceride stream, the triglyceridestream rich in C₁₀ to C₁₄ fatty acid side chains, and a heavy glyceridestream.

In a third aspect of the present invention, the present invention may bebroadly characterized as providing a process for producing a linearhydrocarbon for use in producing a linear alkylbenzene surfactant by:passing a renewable glyceride feedstock to a separation zone configuredto separate the renewable glyceride feedstock into a light glyceridestream, a triglyceride stream rich in C₁₀ to C₁₄ fatty acid side chains,and a heavy glyceride stream; recovering at least one of the heavyglyceride stream and the light glyceride stream to be used as vegetableoil; passing the triglyceride stream rich in C₁₀ to C₁₄ fatty acid sidechains to a deoxygenation zone having a catalyst and being operatedunder deoxygenation conditions to provide a paraffin hydrocarbon stream;passing the paraffin hydrocarbon stream to a dehydrogenation zone toprovide an olefin hydrocarbon stream; and, passing the olefinhydrocarbon stream and an aromatic hydrocarbon stream comprising benzeneto an alkylation zone having an alkylation catalyst and being operatedunder alkylation conditions to provide an alkyl benzene product stream.

In various embodiments of the present invention, the separation zonecomprises a fractionation column.

In some embodiments of the present invention, the separation zonecomprises a crystallizer.

Additional aspects, embodiments, and details of the invention which maybe combined in any manner are set forth in the following detaileddescription of the invention.

BRIEF DESCRIPTION OF THE DRAWING

One or more exemplary embodiments of the present invention will bedescribed below in conjunction with the following drawing FIGURE, inwhich:

The FIGURE shows a processes flow diagram according to one or moreembodiments of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

As mentioned above, various processes have been invented to produce C₁₀to C₁₃ normal paraffins from renewable feedstocks for use as a componentin linear alkylbenzenes. In accordance with various embodiments of thepresent invention, in order to minimize the quantity of diesel andnaphtha produced and maximize the quantity of C₁₀ to C₁₃ normalparaffins produced, the renewable feedstocks is separated into differentfractions by some means of separation before converting one fraction tohydrocarbons. Common separation techniques that could be applied includedistillation and crystallization.

With these general principles in mind, one or more embodiments of thepresent invention will be described with the understanding that thefollowing description is not intended to be limiting.

An exemplary process for producing a linear alkylbenzene, paraffin,and/or olefin product is depicted in the FIGURE in which a renewablefeedstock 10 is passed to a separation zone 12. The renewable feedstock10 comprises natural oils. As used herein, natural oils are thosederived from plant or algae matter, and are often referred to asrenewable oils. Natural oils are not based on kerosene or other fossilfuels. In certain embodiments, the natural oils include, but are notlimited to, one or more of coconut oil, babassu oil, castor oil, algae 1byproduct, beef tallow oil, borage oil, camelina oil, Canola® oil,choice white grease, coffee oil, corn oil, Cuphea Viscosissima oil,evening primrose oil, fish oil, hemp oil, hepar oil, jatropha oil,Lesquerella Fendleri oil, linseed oil, Moringa Oleifera oil, mustardoil, neem oil, palm oil, perilla seed oil, poultry fat, rice bran oil,soybean oil, stillingia oil, sunflower oil, tung oil, yellow grease,cooking oil, and other vegetable, nut, seed oils or animal fats. Othernatural oils will be known to those having ordinary skill in the art.The natural oils typically include triglycerides, free fatty acids, or acombination of both, and other trace compounds. Furthermore, it is alsocontemplated that the oils are microbial oils, which are oils thatproduced by microbes or other organisms, including genetically modifiedor engineered microbes that produce oils, and preferably with desiredside chain lengths.

In various embodiments of the present invention, the renewable feedstock10 preferably comprises an oil having glycerides, preferablytriglycerides having at least one C₁₀ to C₁₄ fatty acid side chain, suchas coconut oil, palm kernel oil, laurel oil, babassu oil, and, mixturesthereof. As is known, the oils comprise glycerides having between oneand three fatty acids bonded together with a glycerol bridge. Asdiscussed in more detail below, when the glycerides and more particularthe fatty acid side chains on the glyceride are converted (e.g.,deoxygenated) into hydrocarbons, the fatty acids will typically convertto paraffins that have either the same or one fewer carbon atoms thanthe fatty acid side chain from which they are derived. Therefore, an oilrich in C₁₀ to C₁₄ free fatty acids and glycerides rich in C₁₀ to C₁₄fatty acid side chains, will produce an effluent having a high amount ofC₁₀ to C₁₄ hydrocarbons via the conversion. By “C₁₀ to C₁₄ fatty acids,”we mean one or more of glycerides having fatty acid side chains having10 to 14 carbon atoms, glycerides having fatty acid side chains whichwhen deoxygenated form paraffins having 10 to 14 carbon atoms (e.g.,coconut oil), and free fatty acids having between 10 and 14 carbonatoms. By “rich in C₁₀ to C₁₄ fatty acids,” we mean that the feedstockcontains at least about 50 wt % of fatty acids having between 10 and 14carbon atoms, or greater than about 55 wt %, or greater than about 60 wt%, or greater than about 65 wt %, or greater than about 65 wt %.

Returning to the FIGURE, the separation zone 12 may include any suitabletechnology or process for separating the glycerides of the renewablefeedstock 10. For example, the separation zone may include afractionation column 14 or a crystallization unit. The particularequipment used to separate the renewable feedstock 10 is not importantto the practicing or understanding of the present invention. Theseparation zone 12 separates the renewable feedstock 10 into at leasttwo streams 16, 18, and preferably at least three streams 16, 18, 19.

The first stream 16 from the separation zone 12 may comprise a lighttriglyceride stream that includes, in one embodiment, triglycerides thatinclude C₈ and lighter fatty acid side chains. The second stream 18 fromthe separation zone 12 may comprise a stream rich in C₁₀ to C₁₄ fattyacid, most preferably rich in glycerides, preferably triglycerides,having one or more C₁₀ to C₁₄ fatty acid side chains. The third stream19 from the separation zone 12 comprises glycerides that include one ormore C₁₄ and heavier fatty acid side chains. It should be appreciatedthat there may be some overlap between the various streams and that thecomposition of the streams refers to the dominant component, and doesnot exclude other components.

The further processing of the first stream 16 and the third stream 19 isnot necessary for the understanding and practicing of the presentinvention. In various embodiments, the first stream 16, the third stream19, or both are used in normal vegetable oil for other use.Alternatively, the first stream 16, the third stream 19, or both can beprocessed and converted into linear hydrocarbons for use, for example asa transportation fuel. Furthermore, if the renewable feedstock 10includes a significant portion of free fatty acids, especially, C₁₀ toC₁₄ free fatty acids, the separation zone 12 may include equipment suchas a column to separate the fatty acids into one or more streams, andequipment such as a column to separate the glycerides into variousstream, which may be combined with the streams of free fatty acids.

Returning to the second stream 18 from the separation zone 12, thesecond stream 18 is passed to a reaction zone 20 to convert theglycerides (and more particularly the fatty acid side chains of theglycerides) into linear hydrocarbons. In a preferred embodiment, thereaction zone 20 comprises a deoxygenation zone in which the fatty acidside chains in the triglycerides and free fatty acids in the secondstream 18 are deoxygenated and converted into linear paraffins, using acatalyst that is suitable for deoxygenation.

As mentioned above, triglycerides are formed by three, typicallydifferent, fatty acid molecules that are bonded together with a glycerolbridge. The glycerol molecule includes three hydroxyl groups (HO—), andeach fatty acid molecule has a carboxyl group (COON)— which shares anoxygen atom with the corresponding hydroxyl group. In triglycerides, thehydroxyl groups of the glycerol join the carboxyl groups of the fattyacids to form ester bonds. Therefore, during deoxygenation, the fattyacids are freed from the triglyceride structure and are converted intolinear paraffins. The glycerol is converted into propane, and the oxygenin the hydroxyl and carboxyl groups is converted into either water orcarbon dioxide. Deoxygenation can occur via two major pathways, wherethe oxygen atoms of the triglyceride either combine with availablehydrogen to form water (H₂O), known as hydrodeoxygenation, or retaintheir linkage to the first carbon of the fatty chain and convert tocarbon dioxide (CO₂) or carbon monoxide (CO), known as decarboxylationand decarbonylation, respectively. Hydrodeoxygenation anddecarboxylation/decarbonylation occur simultaneously and both result inthe fatty acids breaking their links to the three-carbon backbone of thetriglyceride, such that water, carbon oxides, and propane are evolved.With CO, CO₂, H₂O, and H₂ simultaneously present, the Water-Gas shiftreaction will shift CO₂ and H₂ into CO and H₂O, or vice versa, dependingon the catalyst selection and reaction conditions. Once deoxygenated andsaturated, the fatty acid chains of the original triglyceride have beenconverted to long linear paraffin chains (normal alkanes) that are fullyhydrocarbon.

An exemplary deoxygenation zone is disclosed for example in U.S. Pat.No. 8,039,682, the entirety of which is incorporated herein byreference. In general, the deoxygenation zone includes one or morereactors comprising a suitable catalyst(s) for promoting deoxygenationreactions and which may be any of those well known in the art such asnickel or nickel/molybdenum dispersed on a high surface area support.Other catalysts include one or more noble metal catalytic elementsdispersed on a high surface area support. Non-limiting examples of noblemetals include Pt and/or Pd dispersed on gamma-alumina. Generally,deoxygenation conditions include a temperature of about 40 to about 700°C. (104 to 1,292° F.) and a pressure of about 700 to about 21 MPa (100to 3,000 psig). Other operating conditions for the deoxygenation zone 20are well known in the art.

As shown in the FIGURE, a deoxygenation effluent stream 22 may be passedfrom the reaction zone 20 to a separation zone 24 to separate thedesired linear paraffins from the branched compounds, the cycliccompounds and the undesired linear hydrocarbons that may be included inthe deoxygenation effluent stream 22. In one embodiment, the separationzone 24 may comprise a separator 26 and a fractionation column 28. Theseparator 26 can be either a cold or hot separator and is used to removethe byproducts of the deoxygenation zone 20 reactions. If the separator26 comprises a cold separator, a water stream 32 may be removed as aliquid from the bottom of the separator 26. If the separator 26comprises a hot separator is used, water may be removed in a vaporstream 27 from the overhead of the separator 26. In either case, thevapor stream 27 from the separator 26 will comprise at least propane andlight ends, carbon oxides and hydrogen sulfide. Additionally, in eithermode, the vapor stream 27 from the separator 26 may comprise at leastsome water vapor.

The carbon oxides and hydrogen sulfide may be removed from the vaporstream 27 by techniques such as scrubbing. Suitable scrubbing techniquesare described in U.S. Pat. No. 7,982,077 and U.S. Pat. No. 7,982,078each hereby incorporated by reference in its entirety. After the carbonoxides and/or the hydrogen sulfide has been removed from the vaporstream 27, the propane and other light ends may be, for example,directed to an optional steam reforming zone (not shown). If theseparator 26 is operated as a hot separator and water vapor is presentin the separator overhead, the water may be optionally retained in thecarbon oxide and hydrogen sulfide scrubber, condensed from thehydrocarbon stream, or co-fed with the light ends to the steam reformer.

The temperature of the separator 26 may be from about ambienttemperature to about 454° C. (about 850° F.), and the pressure may befrom about 1379 kPa gauge to about 13,790 kPa gauge (200 to about 2,000psig). In one embodiment, the temperature is from about 150° C. to about454° C. (about 300° F. to about 850° F.).

The fractionation column 28 in the separation zone 24 separates thelinear hydrocarbons 30 into one or more streams, for example, a lightends stream 34, a desired paraffin hydrocarbon stream 36, and a heavystream 38. In the present application, the desired paraffin hydrocarbonstream 36 comprises mostly C₁₀ to C₁₃ hydrocarbons, with theunderstanding that some lighter and some heavier components may also becontained therein. Accordingly, in cases in which the desiredhydrocarbon stream 36 comprises mostly C₁₀ to C₁₃ hydrocarbons, thelight hydrocarbon stream 34 may comprises C⁹⁻ hydrocarbons, while theheavy stream 38 may comprises C₁₄₊ hydrocarbons.

The desired paraffin hydrocarbon stream 36 may be passed to adehydrogenation zone 40 to provide an olefin hydrocarbon stream 42.Although not depicted as such, one or more of the streams from thefractionation column 28 may be directed first to a purification zone(not shown) to remove any remaining trace contaminants, such asoxygenates, nitrogen compounds, and sulfur compounds, among others, thatwere not previously removed in the processing steps described above.

In the dehydrogenation zone 40, the desired paraffin hydrocarbon stream36 is dehydrogenated into olefins, preferably predominantlymono-olefins. Typically, dehydrogenation occurs through known catalyticprocesses, such as the commercially popular Pacol process. Conversion istypically less than about 30%, for example less than about 20%, leavinggreater than about 70% paraffins unconverted to olefins. Di-olefins(i.e., dienes) and aromatics are also produced as an undesired result ofthe dehydrogenation reactions. In order to convert the di-olefins tomono-olefins, the dehydrogenation zone 40 may include a selectivehydrogenation zone such as a DeFine® reactor (or a reactor employing aDeFine® process), available from UOP LLC. The hydrogenation unit isconfigured to selectively hydrogenate at least a portion of thedi-olefins. As a result, the olefin stream 42 form the dehydrogenationzone 40 will have an increased mono-olefin concentration. Thedehydrogenation zone 40 may also include a separation zone configured toseparate the desired olefins from the unconverted converted paraffins44, which may be recycled as feed to the dehydrogenation zone 40. Anolefin hydrocarbon stream 42 from the dehydrogenation zone 40 and abenzene stream 46 may be passed to an alkylation zone 48.

The alkylation zone 48 comprises one or more reactors having a catalyst,such as a solid acid catalyst, that supports alkylation of the benzenewith the mono-olefins. Hydrogen fluoride (HF) and aluminum chloride(AlCl₃) are two major catalysts in commercial use for the alkylation ofbenzene with linear mono-olefins and may be used in the alkylation zone48. Additional catalysts include zeolite-based or fluoridate silicaalumina-based solid bed alkylation catalysts (for example, FAU, MOR,UZM-8, Y, X RE exchanged Y, RE exchanged X, amorphous silica-alumina,and mixtures thereof, and others known in the art). As a result ofalkylation, alkylbenzene, typically called linear alkylbenzene isproduced. An effluent from the alkylation zone 48 may include unreactedbenzene and other compounds which may be separated from an alkylbenzeneproduct stream 50.

The alkylbenzene product stream 50 may be passed to a sulfonation zone52 in which the linear alkylbenzene will be sulfonated and neutralizedwith sodium hydroxide to produce a surfactant product stream 54.

In the various processes according to the present invention, yieldlosses and undesired conversion costs associated with processingundesirable fatty acid side chains and free fatty acids have beenminimized due to the separation of the feedstock prior to converting itinto hydrocarbons. Thus, the conversion into hydrocarbons will befocused on those molecules most capable of forming hydrocarbons in thedesired or target hydrocarbon product range—in the case of linearalkylbenzene C₁₀ to C₁₃ hydrocarbons. Additionally, further benefits canbe obtained by selecting an oil as a feedstock that is rich in fattyacids that may be converted into hydrocarbons within the desired ortarget hydrocarbon product range.

It should be appreciated and understood by those of ordinary skill inthe art that various other components such as valves, pumps, filters,coolers, etc. were not shown in the drawings as it is believed that thespecifics of same are well within the knowledge of those of ordinaryskill in the art and a description of same is not necessary forpracticing or understating the embodiments of the present invention.

SPECIFIC EMBODIMENTS

While the following is described in conjunction with specificembodiments, it will be understood that this description is intended toillustrate and not limit the scope of the preceding description and theappended claims.

A first embodiment of the invention is a process for producing a linearhydrocarbon for use in producing a linear alkyl benzene surfactant, theprocess comprising separating a renewable feedstock in a separation zoneinto a glyceride stream rich C₁₀ to C₁₄ fatty acids and at least oneother glyceride steam; deoxygenating the glyceride stream rich inglycerides with C₁₀ to C₁₄ fatty acid side chains in a deoxygenationzone having a catalyst and being operated under deoxygenation conditionsto provide a paraffin hydrocarbon stream, dehydrogenating the paraffinhydrocarbon stream in a dehydrogenation zone to provide an olefinhydrocarbon stream, and, alkylating the olefin hydrocarbon stream withan aromatic hydrocarbon stream in an alkylation zone having analkylation catalyst and being operated under alkylation conditions toprovide an alkyl benzene product stream. An embodiment of the inventionis one, any or all of prior embodiments in this paragraph up through thefirst embodiment in this paragraph wherein the separation zone comprisesat least one fractionation column. An embodiment of the invention isone, any or all of prior embodiments in this paragraph up through thefirst embodiment in this paragraph wherein the fractionation zoneprovides the glyceride stream rich in glycerides with C₁₀ to C₁₄ fattyacid side chains, a heavy glyceride steam, and a light glyceride stream.An embodiment of the invention is one, any or all of prior embodimentsin this paragraph up through the first embodiment in this paragraphfurther comprising recovering at least one of the heavy glyceride streamand the light glyceride stream to be used as vegetable oil. Anembodiment of the invention is one, any or all of prior embodiments inthis paragraph up through the first embodiment in this paragraph furthercomprising recovering both the heavy glyceride steam and the lightglyceride stream to be used as vegetable oil. An embodiment of theinvention is one, any or all of prior embodiments in this paragraph upthrough the first embodiment in this paragraph, wherein the renewableglyceride feedstock comprises an oil rich in glycerides with C₁₀ to C₁₄fatty acid side chains. An embodiment of the invention is one, any orall of prior embodiments in this paragraph up through the firstembodiment in this paragraph, wherein the oil rich in glycerides withC₁₀ to C₁₄ fatty acid side chains is selected from the group consistingof: coconut oil; palm kernel oil; laurel oil; babassu oil; microbialoils; and, mixtures thereof. An embodiment of the invention is one, anyor all of prior embodiments in this paragraph up through the firstembodiment in this paragraph further comprising sulfonating the alkylbenzene product stream to provide a surfactant product.

A second embodiment of the invention is a process for producing a linearhydrocarbon for use in producing a linear alkyl benzene surfactant, theprocess comprising passing a renewable glyceride feedstock to aseparation zone to separate the renewable glyceride feedstock into aglyceride stream rich in glycerides with C₁₀ to C₁₄ fatty acid sidechains and at least one other glyceride steam, passing the glyceridestream rich in glycerides with C₁₀ to C₁₄ fatty acid side chains to adeoxygenation zone having a catalyst and being operated underdeoxygenation conditions to provide a paraffin hydrocarbon stream;passing the paraffin hydrocarbon stream to a dehydrogenation zone toprovide an olefin hydrocarbon stream, and, passing the olefinhydrocarbon stream and an aromatic hydrocarbon stream comprising benzeneto an alkylation zone having an alkylation catalyst and being operatedunder alkylation conditions to provide an alkyl benzene product stream.An embodiment of the invention is one, any or all of prior embodimentsin this paragraph up through the second embodiment in this paragraphfurther comprising sulfonating the alkyl benzene product stream toprovide a surfactant product. An embodiment of the invention is one, anyor all of prior embodiments in this paragraph up through the secondembodiment in this paragraph wherein the separation zone provides thetriglyceride stream rich in C₁₀ to C₁₄ fatty acids, a heavy glyceridesteam, and a light glyceride stream. An embodiment of the invention isone, any or all of prior embodiments in this paragraph up through thesecond embodiment in this paragraph further comprising recovering atleast one of the heavy glyceride stream and the light glyceride streamto be used as vegetable oil. An embodiment of the invention is one, anyor all of prior embodiments in this paragraph up through the secondembodiment in this paragraph further comprising separating the paraffinhydrocarbon stream into at a C₁₀ to C₁₃ hydrocarbon stream and at leastone other paraffin stream; and, passing the C₁₀ to C₁₃ hydrocarbonstream to a dehydrogenation zone. An embodiment of the invention is one,any or all of prior embodiments in this paragraph up through the secondembodiment in this paragraph, wherein the renewable glyceride feedstockis selected from the group consisting of: coconut oil; palm kernel oil;laurel oil; babassu oil; microbial oils; and mixtures thereof. Anembodiment of the invention is one, any or all of prior embodiments inthis paragraph up through the second embodiment in this paragraph,wherein the renewable glyceride feedstock comprises an oil rich inglycerides having C₁₀ to C₁₄ fatty acid side chains. An embodiment ofthe invention is one, any or all of prior embodiments in this paragraphup through the second embodiment in this paragraph wherein theseparation zone comprises a fractionation column. An embodiment of theinvention is one, any or all of prior embodiments in this paragraph upthrough the second embodiment in this paragraph wherein thefractionation column provides a light glyceride stream, the glyceridestream rich in glycerides with C₁₀ to C₁₄ fatty acid side chains, and aheavy glyceride stream.

A third embodiment of the invention is a process for producing a linearhydrocarbon for use in producing a linear alkyl benzene surfactant, theprocess comprising passing a renewable glyceride feedstock to aseparation zone configured to separate the renewable glyceride feedstockinto a light glyceride stream, a glyceride stream rich in glycerideswith C₁₀ to C₁₄ fatty acid side chains, and a heavy glyceride stream,recovering at least one of the heavy glyceride stream and the lightglyceride stream to be used as vegetable oil; passing the glyceridestream rich in glycerides with C₁₀ to C₁₄ fatty acid side chains to adeoxygenation zone having a catalyst and being operated underdeoxygenation conditions to provide a paraffin hydrocarbon stream,passing the paraffin hydrocarbon stream to a dehydrogenation zone toprovide an olefin hydrocarbon stream, and, passing the olefinhydrocarbon stream and an aromatic hydrocarbon stream comprising benzeneto an alkylation zone having an alkylation catalyst and being operatedunder alkylation conditions to provide an alkyl benzene product stream.An embodiment of the invention is one, any or all of prior embodimentsin this paragraph up through the third embodiment in this paragraphwherein the separation zone comprises a crystallizer. An embodiment ofthe invention is one, any or all of prior embodiments in this paragraphup through the third embodiment in this paragraph further comprisingseparating the paraffin hydrocarbon stream into at a C₁₀ to C₁₃hydrocarbon stream and at least one other paraffin stream; and, passingthe C₁₀ to C₁₃ hydrocarbon stream to a dehydrogenation zone.

Without further elaboration, it is believed that using the precedingdescription that one skilled in the art can utilize the presentinvention to its fullest extent and easily ascertain the essentialcharacteristics of this invention, without departing from the spirit andscope thereof, to make various changes and modifications of theinvention and to adapt it to various usages and conditions. Thepreceding preferred specific embodiments are, therefore, to be construedas merely illustrative, and not limiting the remainder of the disclosurein any way whatsoever, and that it is intended to cover variousmodifications and equivalent arrangements included within the scope ofthe appended claims.

In the foregoing, all temperatures are set forth in degrees Celsius and,all parts and percentages are by weight, unless otherwise indicated.

While at least one exemplary embodiment has been presented in theforegoing detailed description of the invention, it should beappreciated that a vast number of variations exist. It should also beappreciated that the exemplary embodiment or exemplary embodiments areonly examples, and are not intended to limit the scope, applicability,or configuration of the invention in any way. Rather, the foregoingdetailed description will provide those skilled in the art with aconvenient road map for implementing an exemplary embodiment of theinvention, it being understood that various changes may be made in thefunction and arrangement of elements described in an exemplaryembodiment without departing from the scope of the invention as setforth in the appended claims and their legal equivalents.

The invention claimed is:
 1. A process for producing a linearmono-olefin hydrocarbon stream for use in producing a linear alkylbenzene product stream, the process comprising: distilling a renewablefeedstock comprising one or more natural oils derived from plant oralgae matter in a separation zone to provide a light glyceride streamthat includes C₈ and lighter fatty acid side chains, a glyceride streamrich in glycerides with C₁₀ to C₁₄ fatty acid side chains, and at leastone other glyceride stream; deoxygenating the glyceride stream rich inglycerides with C₁₀ to C₁₄ fatty acid side chains in a deoxygenationzone having a catalyst to provide a paraffin hydrocarbon stream;dehydrogenating the paraffin hydrocarbon stream in a dehydrogenationzone to provide a linear mono-olefin hydrocarbon stream; and alkylatingthe linear mono-olefin hydrocarbon stream with benzene in an alkylationzone having an alkylation catalyst to provide a linear alkyl benzeneproduct stream.
 2. The process of claim 1 wherein the separation zonecomprises at least one fractionation column.
 3. The process of claim 1wherein the at least one other glyceride stream comprises a heavyglyceride stream that includes one or more C₁₄ and heavier fatty acidside chains.
 4. The process of claim 3 further comprising: recovering atleast one of the heavy glyceride stream and the light glyceride streamto be used as vegetable oil.
 5. The process of claim 3 furthercomprising: recovering both the heavy glyceride stream and the lightglyceride stream to be used as vegetable oil.
 6. The process of claim 1,wherein the renewable feedstock comprises a natural oil rich inglycerides with C₁₀ to C₁₄ fatty acid side chains.
 7. The process ofclaim 6, wherein the natural oil rich in glycerides with C₁₀ to C₁₄fatty acid side chains is selected from the group consisting of: coconutoil; palm kernel oil; laurel oil; babassu oil; microbial oils; andmixtures thereof.
 8. The process of claim 1 further comprising:sulfonating the linear alkyl benzene product stream to provide asurfactant product.
 9. A process for producing a linear mono-olefinhydrocarbon stream for use in producing a linear alkyl benzene productstream, the process comprising: passing a renewable glyceride feedstockto a separation zone; distilling the renewable glyceride feedstock toprovide a light glyceride stream that includes C₈ and lighter fatty acidside chains, a glyceride stream rich in glycerides with C₁₀ to C₁₄ fattyacid side chains, and at least one other glyceride stream comprisingglycerides that include one or more C₁₄ and heavier fatty acid sidechains; passing the glyceride stream rich in glycerides with C₁₀ to C₁₄fatty acid side chains to a deoxygenation zone having a catalyst toprovide a paraffin hydrocarbon stream; passing at least a portion of theparaffin hydrocarbon stream to a dehydrogenation zone to provide alinear mono-olefin hydrocarbon stream; passing the linear mono-olefinhydrocarbon stream and benzene to an alkylation zone having analkylation catalyst to provide a linear alkyl benzene product stream;and recovering the light glyceride stream and the at least one otherglyceride stream to be used as a vegetable oil.
 10. The process of claim9 further comprising: sulfonating the linear alkyl benzene productstream to provide a surfactant product.
 11. The process of claim 10,wherein the paraffin hydrocarbon stream comprises C₁₀ to C₁₃hydrocarbons and wherein passing at least a portion of the paraffinhydrocarbon stream to the dehydrogenation zone comprises: separating theparaffin hydrocarbon stream into a C₁₀ to C₁₃ hydrocarbon stream and atleast one other paraffin stream; and passing the C₁₀ to C₁₃ hydrocarbonstream to the dehydrogenation zone.
 12. The process of claim 10, whereinthe renewable glyceride feedstock is selected from the group consistingof: coconut oil; palm kernel oil; laurel oil; babassu oil; microbialoils; and mixtures thereof.
 13. The process of claim 10, wherein therenewable glyceride feedstock comprises an oil rich in glycerides havingC₁₀ to C₁₄ fatty acid side chains.
 14. The process of claim 9 whereinthe separation zone comprises a fractionation column.
 15. A process forproducing a linear mono-olefin hydrocarbon stream for use in producing alinear alkyl benzene product stream, the process comprising: passing arenewable glyceride feedstock to a separation zone; distilling therenewable glyceride feedstock to provide a light glyceride stream thatincludes C₈ and lighter fatty acid side chains, a glyceride stream richin glycerides with C₁₀ to C₁₄ fatty acid side chains, and a heavyglyceride stream; recovering at least one of the heavy glyceride streamand the light glyceride stream to be used as vegetable oil; passing theglyceride stream rich in glycerides with C₁₀ to C₁₄ fatty acid sidechains to a deoxygenation zone having a catalyst to provide a paraffinhydrocarbon stream; passing at least a portion of the paraffinhydrocarbon stream to a dehydrogenation zone to provide a linearmono-olefin hydrocarbon stream; and passing the linear mono-olefinhydrocarbon stream and benzene to an alkylation zone having analkylation catalyst to provide a linear alkyl benzene product stream.16. The process of claim 15, wherein the paraffin hydrocarbon streamcomprises C₁₀ to C₁₃ hydrocarbons and wherein passing at least a portionof the paraffin hydrocarbon stream to the dehydrogenation zonecomprises: separating the paraffin hydrocarbon stream into a C₁₀ to C₁₃hydrocarbon stream and at least one other paraffin stream; and passingthe C₁₀ to C₁₃ hydrocarbon stream to the dehydrogenation zone.